Natural Oil Derivatives Including Primary Amine Functional Groups

ABSTRACT

A compound has Structure I: 
     
       
         
         
             
             
         
       
     
     where R 1  and R 2  independently are C 2 -C 12  alkyl groups, X 1  is a C 4 -C 28  alkyl or alkenyl group, and R 3  is H or is a bis(aminoalkyl)amide group having Structure II: 
     
       
         
         
             
             
         
       
     
     where R 4  and R 5  independently are C 2 -C 12  alkyl groups. The compound may be a reaction product of a metathesized natural oil and a bis(aminoalkyl)amine.

REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Application No.61/779,358 entitled “Natural Oil Derivatives Including Primary AmineFunctional Groups” filed Mar. 13, 2013, which is incorporated byreference in its entirety.

BACKGROUND

Compounds having multiple primary amine functional groups are used in awide variety of applications. Polymeric materials such as polyamides,epoxy polymers, polyureas and other polymers can be formed bycondensation reactions of amine-functionalized monomers such asdiamines, triamines or tetramines with monomers having other functionalgroups. Polyamides typically are formed by reaction of a diamine monomersuch as ethylenediamine or hexamethylenediamine, with a diacid monomersuch as adipic acid or with a diacid chloride monomer such as sebacoylchloride or terephthaloyl chloride. Epoxy polymers typically are formedby reaction of amine-functionalized monomers such as ethylenediamine,triethylene-triamine, diethylenetriamine, hexamethylenetetramine,tetraethylenepentamine, or amine-terminated polymers or prepolymers withmonomers having two or more epoxy groups, such as diglycidyl ethers ofbisphenol A or bisphenol F, tetraglycidyl diamine-diphenylmethane, ormulti-glycidyl ethers of phenol formaldehyde novolac polymers. Polyureastypically are formed by reaction of a diamine or triamine monomer with adiisocyanate monomer.

Compounds having multiple primary amine functional groups also are usedto form dendritic molecules. Dendritic molecules may be used assolubility enhancers, as catalyst supports, as immunoassay components,and as precursors for advanced materials. Species of the poly(amidoamine) (PAMAM) class of dendrimers typically are formed by alternatingreaction of ethylenediamine and methyl acrylate. Examples of PAMAMdendrimers include but are not limited to [NH₂(CH₂)₂NH₂]:(G=0); dendriPAMAM(NH₂)₄ and its associated higher generation molecules.

The physical and chemical properties of polymers and of dendriticmolecules are affected by the chemical structures of the building blocksused to prepare the polymers and/or dendritic molecules. Alteration ofthe chemical structure, size and/or concentration of these buildingblocks can allow for modification of the properties of the polymer ordendritic molecule.

It is desirable to expand the chemical structures present in compoundshaving multiple primary amine functional groups, so as to expand theuseful properties that can be provided by polymers or dendriticmolecules formed from the compounds. With regard to polymers, forexample, properties such as flexibility, toughness, etc. can beincreased by incorporating chemical groups that lower the modulus orthat can absorb energy, respectively. This expansion of chemicalstructures may be accomplished through post-polymerization processing,such as reaction with other reagents or blending with other polymers. Itis especially desirable, however, to expand the chemical structures byintroducing new chemical structures in the monomeric building blocksfrom which the polymer is formed. With regard to dendritic molecules,properties such as solubility, chemical reactivity, density, etc. can bechanged by incorporating branches having different chain lengths andsubstitution points.

One potential approach to altering the chemical structure of compoundshaving multiple primary amine functional groups is to form the compoundsfrom renewable feedstocks. Renewable feedstocks, such as fatty acids orfatty esters derived from natural oils, have opened new possibilitiesfor the development of a variety of industrially useful substances,including specialty chemicals and intermediates. For example, renewablefeedstocks can be used to prepare compounds having combinations ofproperties that were not available with conventional petroleumfeedstocks. In another example, renewable feedstocks can be used toprepare compounds more efficiently, without requiring undesirablereagents or solvents, and/or with decreased amounts of waste or sideproducts.

It would be desirable to provide compounds having multiple primary aminefunctional groups that include previously unavailable chemicalstructures. Preferably such compounds can be used as substitutes forconventional amine-functionalized compounds, while providing an increasein the renewable content of the final product formed using thecompounds. Preferably such compounds can provide useful combinations ofproperties that are difficult to obtain using compounds formed fromconventional petroleum feedstocks.

SUMMARY

The scope of the present invention is defined solely by the appendedclaims, and is not affected to any degree by the statements within thissummary.

In one aspect, a compound is provided that has Structure I:

where R₁ and R₂ independently are C₂-C₁₂ alkyl groups, X₁ is a C₄-C₂₈alkyl or alkenyl group, and R₃ is H or is a bis(aminoalkyl)amide grouphaving Structure II:

where R₄ and R₅ independently are C₂-C₁₂ alkyl groups.

In another aspect, an (aminoalkyl)amide composition is provided thatincludes the reaction product of a metathesized natural oil and abis(aminoalkyl)amine.

In another aspect, a method of making an (aminoalkyl)amide compositionis provided that includes forming a reaction mixture including ametathesized natural oil and a bis(aminoalkyl)amine, and forming aproduct mixture including an (aminoalkyl)amide formed from themetathesized natural oil and the bis(aminoalkyl)amine.

BRIEF DESCRIPTION OF THE DRAWINGS

The invention can be better understood with reference to the followingdrawings and description. The components in the figures are notnecessarily to scale and are not intended to accurately representmolecules or their interactions, emphasis instead being placed uponillustrating the principles of the invention. Moreover, in the figures,like referenced numerals designate corresponding parts throughout thedifferent views.

FIG. 1 depicts a reaction scheme for a metathesis reaction of a naturaloil.

FIG. 2 depicts a method of making an (aminoalkyl)amide.

FIG. 3 depicts a representative reaction scheme for a method of formingan (aminoalkyl)amide.

DETAILED DESCRIPTION

To provide a clear and more consistent understanding of thespecification and claims of this application, the following definitionsare provided.

The terms “reaction” and “chemical reaction” refer to the conversion ofa substance into a product, irrespective of reagents or mechanismsinvolved.

The term “reaction product” refers to a substance produced from achemical reaction of one or more reactant substances.

The term “alkyl group” refers to a group formed by removing a hydrogenfrom a carbon of an alkane, where an alkane is an acyclic or cycliccompound consisting entirely of hydrogen atoms and saturated carbonatoms.

The term “alkenyl group” refers to a group formed by removing a hydrogenfrom a carbon of an alkene, where an alkene is an acyclic or cycliccompound consisting entirely of hydrogen atoms and carbon atoms, andincluding at least one carbon-carbon double bond. A compound containingan alkenyl group is conventionally referred to as an “unsaturatedcompound”.

The term “functional group” refers to a group that includes one or aplurality of atoms other than hydrogen and sp³ carbon atoms. Examples offunctional groups include but are not limited to hydroxyl (—OH),protected hydroxyl, ether (—C—O—C—), ketone (>C═O), ester (—C(═O)O—C—),carboxylic acid (—C(═O)OH), cyano (—C═N), amido (—C(═O)NH—C—),isocyanate (—N═C═O), urethane (—O—C(═O)—NH—), urea (—NH—C(═O)—NH—),protected amino, thiol (—SH), sulfone, sulfoxide, phosphine, phosphite,phosphate, halide (—X), and the like.

The terms “amine”, “amine group” and “amino group” refer to a groupformed by removing a hydrogen from ammonia (NH₃), from the nitrogen of aprimary amine compound (RNH₂) or from the nitrogen of a secondary aminecompound (R′R″NH), where R, R′ and R″ are organic groups. A primaryamino group may be represented by the structural formula —NH₂, and asecondary amino group may be represented by the structural formula —NRH.

The terms “amide”, “amide group” and “amido group” refer to a groupformed by removing a hydrogen from a carbon atom and/or removing one orboth hydrogens from the nitrogen of an organic amide (R—C(═O)—NH₂)compound, where R is an organic group. A primary amide group may berepresented by the structural formula —C(═O)—NH₂, a secondary amidegroup may be represented by the structural formula —C(═O)—NH—R′, and atertiary amide group may be represented by the structural formula—C(═O)—NR′R″, where R′ and R″ are organic groups.

The term “(aminoalkyl)amide” refers to a compound that includes a leastone alkyl and/or alkenyl group, at least one amide group, and at leastone aminoalkyl group bonded to the amide nitrogen through a C—N bond.

The term “metathesis catalyst” refers to any catalyst or catalyst systemconfigured to catalyze a metathesis reaction.

The terms “metathesize” and “metathesizing” refer to a chemical reactioninvolving a single type of olefin or a plurality of different types ofolefin, which is conducted in the presence of a metathesis catalyst, andwhich results in the formation of at least one new olefin product. Thephrase “metathesis reaction” encompasses cross-metathesis (a.k.a.co-metathesis), self-metathesis, ring-opening metathesis (ROM),ring-opening metathesis polymerizations (ROMP), ring-closing metathesis(RCM), and acyclic diene metathesis (ADMET), and the like, andcombinations thereof.

The terms “natural oils,” “natural feedstocks,” or “natural oilfeedstocks” mean oils derived from plants or animal sources. The term“natural oil” includes natural oil derivatives, unless otherwiseindicated. Examples of natural oils include but are not limited tovegetable oils, algal oils, animal fats, tall oils, derivatives of theseoils, combinations of any of these oils, and the like. Examples ofvegetable oils include but are not limited to canola oil, rapeseed oil,coconut oil, corn oil, cottonseed oil, olive oil, palm oil, peanut oil,safflower oil, sesame oil, soybean oil, sunflower oil, linseed oil, palmkernel oil, tung oil, jatropha oil, mustard oil, camelina oil,pennycress oil, castor oil, and the like, and combinations thereof.Examples of animal fats include but are not limited to lard, tallow,poultry fat, yellow grease, fish oil, and the like, and combinationsthereof. Tall oils are by-products of wood pulp manufacture. A naturaloil may be refined, bleached, and/or deodorized.

The term “natural oil derivatives” refers to compounds or mixtures ofcompounds derived from one or more natural oils using any one orcombination of methods known in the art. Such methods include but arenot limited to saponification, transesterification, esterification,hydrogenation (partial or full), isomerization, oxidation, reduction,and the like, and combinations thereof. Examples of natural oilderivatives include but are not limited to gums, phospholipids,soapstock, acidulated soapstock, distillate or distillate sludge, fattyacids and fatty acid alkyl esters such as 2-ethylhexyl ester,hydroxy-substituted variations thereof of the natural oil, and the like,and combinations thereof. For example, the natural oil derivative may bea fatty acid methyl ester (FAME) derived from the glyceride of thenatural oil.

The term “metathesized natural oil” refers to the metathesis reactionproduct of a natural oil in the presence of a metathesis catalyst, wherethe metathesis product includes a new olefinic compound. A metathesizednatural oil may include a reaction product of two triglycerides in anatural feedstock (self-metathesis) in the presence of a metathesiscatalyst, where each triglyceride has an unsaturated carbon-carbondouble bond, and where the reaction product includes a “natural oiloligomer” having a new mixture of olefins and esters that may includeone or more of metathesis monomers, metathesis dimers, metathesistrimers, metathesis tetramers, metathesis pentamers, and higher ordermetathesis oligomers (e.g., metathesis hexamers). A metathesized naturaloil may include a reaction product of a natural oil that includes morethan one source of natural oil (e.g., a mixture of soybean oil and palmoil). A metathesized natural oil may include a reaction product of anatural oil that includes a mixture of natural oils and natural oilderivatives. A metathesized natural oil may include a cross-metathesisreaction product of a natural oil with another substance having acarbon-carbon double bond, such as an olefin or ethylene.

Compounds having a plurality of primary amine functional groups may beformed from a renewable feedstock, such as a renewable feedstock formedthrough metathesis reactions of natural oils and/or their fatty acid orfatty ester derivatives. When compounds containing a carbon-carbondouble bond undergo metathesis reactions in the presence of a metathesiscatalyst, some or all of the original carbon-carbon double bonds arebroken, and new carbon-carbon double bonds are formed. The products ofsuch metathesis reactions include carbon-carbon double bonds indifferent locations, which can provide unsaturated organic compoundshaving useful chemical structures. Renewable feedstocks for compoundshaving a plurality of primary amine functional groups may includeunsaturated compounds having an internal carbon-carbon double bond.

Compounds having a plurality of primary amine functional groups may beused as monomers in polymerization reactions. The use of a monomercontaining a metathesized natural oil derivative can provide additionaloptions for providing polymeric materials having useful combinations ofproperties, including but not limited to mechanical properties,crosslink density, and post-polymerization reactivity. The compoundshaving a plurality of primary amine functional groups also may be usedas intermediates for preparing larger compounds through the reaction ofone or more of the plurality of primary amine functional groups withanother substance. The use of a monomer and/or an intermediatecontaining a metathesized natural oil derivative may provide certainadvantages over commercial monomers and intermediates, including but notlimited to simpler and/or more cost-effective production, reducedvariability, improved sourcing, and increased biorenewability.

A compound having a plurality of primary amine functional groups may bean (aminoalkyl)amide represented by Structure I:

where R₁ and R₂ independently are C₂-C₁₂ alkyl groups, X₁ is a C₄-C₂₈alkyl or alkenyl group, and R₃ is selected from the group consisting ofH and a N,N-bis(aminoalkyl)amide group represented by Structure II:

where R₄ and R₅ independently are C₂-C₂ alkyl groups.

Preferably R₁, R₂, R₄ and R₅ independently are C₂-C₁₀ alkyl groups,C₂-C₈ alkyl groups, C₂-C₆ alkyl groups or C₂-C₄ alkyl groups. In oneexample, R₁, R₂, R₄ and R₅ are the same, and are a C₂-C₁₀ alkyl group, aC₂-C₈ alkyl group, a C₂-C₆ alkyl group, or a C₂-C₄ alkyl group.

Preferably X₁ is a C₈-C₂₂ alkyl or alkenyl group, or a C₁₀-C₁₆ alkyl oralkenyl group. X₁ may be derived from a natural oil, and preferably isderived from a metathesized natural oil.

In one example, R₁ and R₂ are C₂ alkyl groups, and R₃ is H. A compoundhaving a plurality of primary amine functional groups according to thisexample may be a bis(aminoethyl)amide represented by Structure III:

where X₂ is a C₄-C₂₈ alkyl or alkenyl group. Preferably X₂ is a C₈-C₂₂alkyl or alkenyl group, or a C₁₀-C₁₆ alkyl or alkenyl group. X₂ may bederived from a natural oil, and preferably is derived from ametathesized natural oil.

In another example, R₁ and R₂ are C₂ alkyl groups, R₃ is thebis(aminoalkyl)amide group represented by Structure (II), and R₄ and R₅are C₂ alkyl groups. A compound having a plurality of primary aminefunctional groups according to this example may be atetra(aminoethyl)diamide represented by Structure IV:

where X₃ is a C₄-C₂₈ alkenyl group. Preferably X₃ is a C₈-C₂₂ alkyl oralkenyl group, or a C₁₀-C₁₆ alkyl or alkenyl group. X₃ may be derivedfrom a natural oil, and preferably is derived from a metathesizednatural oil.

Preferably the compound having a plurality of primary amine functionalgroups is derived from a natural oil. More preferably the compoundhaving a plurality of primary amine functional groups is derived from ametathesized natural oil. Preferably the compound having a plurality ofprimary amine functional groups is the reaction product of ametathesized natural oil and a bis(aminoalkyl)amine. In one example, thereaction product of a metathesized natural oil and abis(aminoalkyl)amine may be represented by Structure I, III or IV,above.

The metathesized natural oil used to form the compound having aplurality of primary amine functional groups may be the product of ametathesis reaction of a natural oil in the presence of a metathesiscatalyst. The metathesis catalyst in this reaction may include anycatalyst or catalyst system that catalyzes a metathesis reaction. Anyknown metathesis catalyst may be used, alone or in combination with oneor more additional catalysts. Examples of metathesis catalysts andprocess conditions are described in paragraphs [0069]-[0155] of US2011/0160472, incorporated by reference herein in its entirety, exceptthat in the event of any inconsistent disclosure or definition from thepresent specification, the disclosure or definition herein shall bedeemed to prevail. A number of the metathesis catalysts described in US2011/0160472 are presently available from Materia, Inc. (Pasadena,Calif.).

In some embodiments, the metathesis catalyst includes a transitionmetal. In some embodiments, the metathesis catalyst includes ruthenium.In some embodiments, the metathesis catalyst includes rhenium. In someembodiments, the metathesis catalyst includes tantalum. In someembodiments, the metathesis catalyst includes nickel. In someembodiments, the metathesis catalyst includes tungsten. In someembodiments, the metathesis catalyst includes molybdenum.

In some embodiments, the metathesis catalyst includes a rutheniumcarbene complex and/or an entity derived from such a complex. In someembodiments, the metathesis catalyst includes a material selected fromthe group consisting of a ruthenium vinylidene complex, a rutheniumalkylidene complex, a ruthenium methylidene complex, a rutheniumbenzylidene complex, and combinations thereof, and/or an entity derivedfrom any such complex or combination of such complexes. In someembodiments, the metathesis catalyst includes a ruthenium carbenecomplex including at least one phosphine ligand and/or an entity derivedfrom such a complex. In some embodiments, the metathesis catalystincludes a ruthenium carbene complex including at least onetricyclohexylphosphine ligand and/or an entity derived from such acomplex. In some embodiments, the metathesis catalyst includes aruthenium carbene complex including at least two tricyclohexylphosphineligands [e.g., (PCy₃)₂Cl₂Ru═CH—CH═C(CH₃)₂, etc.] and/or an entityderived from such a complex. In some embodiments, the metathesiscatalyst includes a ruthenium carbene complex including at least oneimidazolidine ligand and/or an entity derived from such a complex. Insome embodiments, the metathesis catalyst includes a ruthenium carbenecomplex including an isopropyloxy group attached to a benzene ringand/or an entity derived from such a complex.

In some embodiments, the metathesis catalyst includes a Grubbs-typeolefin metathesis catalyst and/or an entity derived therefrom. In someembodiments, the metathesis catalyst includes a first-generationGrubbs-type olefin metathesis catalyst and/or an entity derivedtherefrom. In some embodiments, the metathesis catalyst includes asecond-generation Grubbs-type olefin metathesis catalyst and/or anentity derived therefrom. In some embodiments, the metathesis catalystincludes a first-generation Hoveda-Grubbs-type olefin metathesiscatalyst and/or an entity derived therefrom. In some embodiments, themetathesis catalyst includes a second-generation Hoveda-Grubbs-typeolefin metathesis catalyst and/or an entity derived therefrom. In someembodiments, the metathesis catalyst includes one or a plurality of theruthenium carbene metathesis catalysts sold by Materia, Inc. ofPasadena, Calif. and/or one or more entities derived from suchcatalysts. Representative metathesis catalysts from Materia, Inc. foruse in accordance with the present teachings include but are not limitedto those sold under the following product numbers as well ascombinations thereof: product no. C823 (CAS no. 172222-30-9), productno. C848 (CAS no. 246047-72-3), product no. C601 (CAS no. 203714-71-0),product no. C627 (CAS no. 301224-40-8), product no. C571 (CAS no.927429-61-6), product no. C598 (CAS no. 802912-44-3), product no. C793(CAS no. 927429-60-5), product no. C801 (CAS no. 194659-03-9), productno. C827 (CAS no. 253688-91-4), product no. C884 (CAS no. 900169-53-1),product no. C833 (CAS no. 1020085-61-3), product no. C859 (CAS no.832146-68-6), product no. C711 (CAS no. 635679-24-2), product no. C933(CAS no. 373640-75-6).

In some embodiments, the metathesis catalyst includes a molybdenumand/or tungsten carbene complex and/or an entity derived from such acomplex. In some embodiments, the metathesis catalyst includes aSchrock-type olefin metathesis catalyst and/or an entity derivedtherefrom. In some embodiments, the metathesis catalyst includes ahigh-oxidation-state alkylidene complex of molybdenum and/or an entityderived therefrom. In some embodiments, the metathesis catalyst includesa high-oxidation-state alkylidene complex of tungsten and/or an entityderived therefrom. In some embodiments, the metathesis catalyst includesmolybdenum (VI). In some embodiments, the metathesis catalyst includestungsten (VI). In some embodiments, the metathesis catalyst includes amolybdenum- and/or a tungsten-containing alkylidene complex of a typedescribed in one or more of (a) Angew. Chem. Int. Ed. Engl., 2003, 42,4592-4633; (b) Chem. Rev., 2002, 102, 145-179; and/or (c) Chem. Rev.,2009, 109, 3211-3226, each of which is incorporated by reference hereinin its entirety, except that in the event of any inconsistent disclosureor definition from the present specification, the disclosure ordefinition herein shall be deemed to prevail.

Metathesis is a catalytic reaction that involves the interchange ofalkylidene units among compounds containing one or more double bonds(i.e., olefinic compounds) via the formation and cleavage of thecarbon-carbon double bonds. The metathesis reaction of a natural oilcontaining unsaturated polyol esters can produce oligomers of theunsaturated polyol esters. The resulting oligomers typically contain amixture of olefins and esters that may include one or more of metathesismonomers, metathesis dimers, metathesis trimers, metathesis tetramers,metathesis pentamers, and higher order metathesis oligomers (e.g.,metathesis hexamers, etc.). FIG. 1 depicts chemical structures andreaction schemes related to a metathesis reaction 100 of a natural oil110, producing metathesis dimer 120, metathesis trimer 130 and higherorder metathesis oligomers (not pictured). A metathesis dimer refers toa compound formed when two unsaturated polyol ester molecules arecovalently bonded to one another by a metathesis reaction. The molecularweight of the metathesis dimer typically is greater than the molecularweight of the individual unsaturated polyol ester molecules from whichthe dimer is formed. A metathesis trimer refers to a compound formedwhen three unsaturated polyol ester molecules are covalently bondedtogether by metathesis reactions. A metathesis trimer may be formed bythe cross-metathesis of a metathesis dimer with an unsaturated polyolester. A metathesis tetramer refers to a compound formed when fourunsaturated polyol ester molecules are covalently bonded together bymetathesis reactions. A metathesis tetramer may be formed by thecross-metathesis of a metathesis trimer with an unsaturated polyolester. Metathesis tetramers may also be formed, for example, by thecross-metathesis of two metathesis dimers. Higher order metathesisoligomers (such as metathesis pentamers, metathesis hexamers, and thelike) also may be formed.

The metathesized natural oil may be derived from natural oils such asvegetable oil, algal oil, animal fat, tall oil, derivatives of theseoils, or mixtures thereof. Examples of vegetable oils include but arenot limited to canola oil, rapeseed oil, coconut oil, corn oil,cottonseed oil, olive oil, palm oil, peanut oil, safflower oil, sesameoil, soybean oil, sunflower oil, linseed oil, palm kernel oil, tung oil,jatropha oil, mustard oil, camelina oil, pennycress oil, castor oil, andthe like, and combinations thereof. Examples of animal fats include butare not limited to lard, tallow, poultry fat, yellow grease, fish oil,and the like, and combinations thereof. Examples of natural oilderivatives include but are not limited to metathesis oligomers, gums,phospholipids, soapstock, acidulated soapstock, distillate or distillatesludge, fatty acids and fatty acid alkyl ester such as 2-ethylhexylester, hydroxyl-substituted variations of the natural oil, and the like,and combinations thereof. For example, the natural oil derivative may bea fatty acid methyl ester (FAME) derived from the glyceride of thenatural oil.

The natural oil may include canola or soybean oil, such as refined,bleached and deodorized soybean oil (i.e., RBD soybean oil). Soybean oiltypically includes about 95 percent by weight (wt %) or greater (e.g.,99 wt % or greater) triglycerides of fatty acids. Major fatty acids inthe polyol esters of soybean oil include but are not limited tosaturated fatty acids such as palmitic acid (hexadecanoic acid) andstearic acid (octadecanoic acid), and unsaturated fatty acids such asoleic acid (9-octadecenoic acid), linoleic acid (9,12-octadecadienoicacid), and linolenic acid (9,12,15-octadecatrienoic acid).

The metathesized natural oil may be a metathesized vegetable oil, ametathesized algal oil, a metathesized animal fat, a metathesized talloil, a metathesized derivatives of these oils, or a mixture thereof. Forexample, a metathesized vegetable oil may include metathesized canolaoil, metathesized rapeseed oil, metathesized coconut oil, metathesizedcorn oil, metathesized cottonseed oil, metathesized olive oil,metathesized palm oil, metathesized peanut oil, metathesized saffloweroil, metathesized sesame oil, metathesized soybean oil, metathesizedsunflower oil, metathesized linseed oil, metathesized palm kernel oil,metathesized tung oil, metathesized jatropha oil, metathesized mustardoil, metathesized camelina oil, metathesized pennycress oil,metathesized castor oil, metathesized derivatives of these oils, ormixtures thereof. In another example, the metathesized natural oil mayinclude a metathesized animal fat, such as metathesized lard,metathesized tallow, metathesized poultry fat, metathesized fish oil,metathesized derivatives of these oils, or mixtures thereof.

FIG. 2 depicts a method 200 of making an (aminoalkyl)amide composition.The method 200 includes forming 201 a reaction mixture 210 containing ametathesized natural oil 212 and a bis(aminoalkyl)amine 214; forming 202a product mixture 220 containing an (aminoalkyl)amide 222 formed fromthe metathesized natural oil 212 and the bis(aminoalkyl)amine 214; andoptionally isolating 203 an (aminoalkyl)amide 222 from the productmixture 220.

The metathesized natural oil 212 may be a metathesized vegetable oil, ametathesized algal oil, a metathesized animal fat, a metathesized talloil, a metathesized derivatives of these oils, or a mixture thereof, asdescribed above. Preferably the metathesized natural oil 212 includesmetathesized soybean oil (MSBO).

The bis(aminoalkyl)amine 214 may be any secondary amine that includestwo aminoalkyl groups bonded to the secondary amine nitrogen through C—Nbonds. The bis(aminoalkyl)amine 214 may be represented by Structure V:

where R₁ and R₂ are as described above regarding Structure I. The twoaminoalkyl groups (—R₁—NH₂ and —R₂—NH₂) may be the same, or they may bedifferent. The primary amine group may be at any of a number ofpositions within the aminoalkyl group. Preferably at least one of theaminoalkyl groups is a ω-aminoalkyl group, in which the primary aminegroup is at the end of the aminoalkyl group opposite that of the C—Nbond to the secondary amine nitrogen. Examples of bis(aminoalkyl)aminesinclude bis(2-aminopropyl)amine and N-2-aminopropyl-N-aminoethylamine.Examples of bis(w-aminoalkyl)amines include but are not limited todiethylenetriamine. Preferably the bis(aminoalkyl)amine 214 includesdiethylene triamine.

In some embodiments, the amount of bis(aminoalkyl)amine 214 present inthe reaction mixture may be between about 0.1 percent by weight (wt %)and about 30 wt % of the metathesized natural oil in the reactionmixture. The amount of bis(aminoalkyl)amine in the reaction mixture alsomay be expressed in terms of the ratio of equivalents of secondary aminein the bis(aminoalkyl)amine to ester equivalents in the metathesizednatural oil (A:E ratio). For example, in some embodiments, the A:E ratiomay be between about 1:100 and about 10:1, or between about 1:10 andabout 5:1. In another example, the A:E ratio may be about 1:3, about2:3, about 1:2, or about 1:1.

The reaction mixture 210 may include one or more other substances, suchas a solvent, a base and/or a catalyst, in addition to the metathesizednatural oil 212 and the bis(aminoalkyl)amine 214. The metathesizednatural oil 212, bis(aminoalkyl)amine 214 and optional other substancesmay be combined simultaneously or in any order.

In some embodiments, a base may be present in the reaction mixture toincrease the rate of reaction between the bis(aminoalkyl)amine and themetathesized natural oil. Examples of bases include but are not limitedto sodium carbonate, lithium carbonate, sodium methoxide, potassiumhydroxide, sodium hydride, potassium butoxide, potassium carbonate, ormixtures of these. The base may be added to the reaction mixture 210neat or as a mixture with a solvent such as water, alcohol, or anotherorganic solvent. In some embodiments, the amount of base in the reactionmixture may be between about 0.1 wt % and about 10 wt % of themetathesized natural oil in the reaction mixture, or between about 1 wt% and about 15 wt % of the metathesized natural oil. In someembodiments, the amount of base in the reaction mixture may be betweenabout 1 wt % and about 10 wt % of the metathesized natural oil, betweenabout 0.1 wt % and about 1.0 wt % of the metathesized natural oil, orbetween about 0.01 wt % and about 0.1 wt % of the metathesized naturaloil.

The forming 202 a product mixture 220 containing an (aminoalkyl)amide222 may include heating the reaction mixture 210. In some embodiments,the rate of reaction between the bis(aminoalkyl)amine 214 and themetathesized natural oil 212 may be increased by heating the reactionmixture, with or without a base, to at least about 100° C., at leastabout 120° C., at least about 140° C., at least about 160° C., orbetween about 100° C. and about 200° C. In some embodiments, thereaction may be carried out at an elevated temperature of between about30 and about 200° C., between about 80 and about 150° C., or betweenabout 100 and about 125° C. In some embodiments, the reaction mixturemay be maintained at the elevated temperature for a time sufficient toform an (aminoalkyl)amide 222, such as between about 1 and about 24hours, or between about 4 and about 24 hours. For example, the reactionmixture may be maintained at the elevated temperature for about 1 hour,about 2 hours, about 4 hours, or about 6 hours. In some embodiments, thereaction may be carried out in an inert atmosphere, such as a nitrogenatmosphere or a noble gas atmosphere. In some embodiments, the reactionmay be carried out in an ambient atmosphere.

The optionally isolating 203 an (aminoalkyl)amide 222 from the productmixture 220 may include removing volatile substances under vacuum. Forexample, the product mixture may be placed under a vacuum for betweenabout 30 minutes and about 1 hour. Volatile substances may include butare not limited to water, solvent, unreacted bis(aminoalkyl)amine,and/or glycerol.

The (aminoalkyl)amide 222 reaction product may have one chemicalstructure, or the reaction product may be a mixture of compounds havingdifferent chemical structures. For example, the (aminoalkyl)amide 222reaction product may include a mixture of compounds represented byStructure I. For a reaction product that includes a mixture of compoundshaving different chemical structures, individual compounds may beisolated from the reaction product, or the reaction product may be usedas a mixture.

FIG. 3 depicts chemical structures and a reaction scheme for an exampleof a method 300 of making an (aminoalkyl)amide composition. The method300 includes forming a reaction mixture 310 containing metathesizedsoybean oil (MSBO) 312 as the metathesized natural oil anddiethylenetriamine 314 as the bis(aminoalkyl)amine. The reaction mixture310 also may include one or more other substances, such as a solvent, abase and/or a catalyst.

Method 300 further includes forming 302 a product mixture 320 containing(aminoethyl)amide species, such as 322 and/or 324. In species 322 and324, w, x, y and z independently are integers from 0 to 18, such thatthe total number of carbon atoms between the amido groups is from 6 to28, and the partially dashed double line indicates that species may ormay not include one or more carbon-carbon double bonds. The forming 302may include heating the reaction mixture as described above, includingmaintaining the reaction mixture at a temperature of from about 30° C.to about 200° C. for a time sufficient to form (aminoalkyl)amidespecies. The tetra(aminoethyl)diamide species 322 andbis(aminoethyl)amide species 324 are exemplary, as the product mixture320 may include a number of different species of (aminoethyl)amidesconsistent with Structure I. Structural variables between the speciesinclude but are not limited to the presence and number of carbon-carbondouble bonds, the number of carbon atoms in the organic group bonded tothe (aminoethyl)amide group(s), and branching.

Method 300 further may include isolating an (aminoethyl)amide species.As noted above, isolating one or both of the (aminoethyl)amide speciesmay include removing volatile substances under vacuum, where thevolatile substances may include but are not limited to water, solvent,unreacted diethylenetriamine 314, and/or glycerol. The optionalisolating may provide a mixture of (aminoalkyl)amide species, or it mayprovide a single (aminoalkyl)amide species.

A compound having a plurality of primary amine functional groups, suchas the reaction product of a metathesized natural oil and abis(aminoalkyl)amine and/or a compound represented by Structure I above,may be used in a polymerization reaction. A monofunctional monomer, suchas a monomer having Structure I in which —R₃ is H, may be used as achain extender in a polymer. A difunctional monomer, such as a monomerhaving Structure I in which —R₃ is a bis(aminoalkyl)amide group, may beused as a crosslinker in a polymer. A mixture of monofunctional anddifunctional monomers may be used to provide both chain extension andcrosslinking features to a polymer.

In one example, the compound having a plurality of primary aminefunctional groups may be reacted with monomers having two or more epoxygroups to form an epoxy polymer. Examples of monomers having two or moreepoxy groups include but are not limited to diglycidyl ethers ofbisphenol A or bisphenol F, tetraglycidyl diamine-diphenylmethane, andmulti-glycidyl ethers of phenol formaldehyde novolac polymers. Thecompound having a plurality of primary amine functional groups mayaccount for all of the amine-functionalized monomer in thepolymerization reaction, or one or more other amine-functionalizedmonomers, such as such as ethylene diamine, triethylenetriamine,diethylenetriamine, hexamethylenetetramine, tetraethylenepentamine oramine-terminated polymers or prepolymers, may be present in thepolymerization.

In another example, the compound having a plurality of primary aminefunctional groups may be reacted with a diacid monomer or a diacidchloride monomer to form a polyamide. Examples of diacid monomersinclude but are not limited to adipic acid. Examples of diacid chloridemonomers include but are not limited to sebacoyl chloride andterephthaloyl chloride. The compound having a plurality of primary aminefunctional groups may account for all of the amine-functionalizedmonomer in the polymerization reaction, or one or more otheramine-functionalized monomers, such as such as ethylenediamine orhexamethylenediamine, may be present in the polymerization.

A compound having a plurality of primary amine functional groups, suchas the reaction product of a metathesized natural oil and abis(aminoalkyl)amine and/or a compound represented by Structure I above,may be used to form a dendritic molecule. In one example, the compoundhaving a plurality of primary amine functional groups may be used as asubstitute for some or all of the ethylenediamine typically used in thesynthesis of PAMAM dendrimers. In another example, the compound having aplurality of primary amine functional groups may be used as the core inthe divergent synthesis of a dendrimer. Reaction of the compound withmethyl acrylate, followed by reaction with ethylenediamine, may providea dendrimer analogous to the PAMAM system, but with a core that is moreflexible and less sterically hindered.

The following examples and representative procedures illustrate featuresin accordance with the present teachings, and are provided solely by wayof illustration. They are not intended to limit the scope of theappended claims or their equivalents, and numerous variations can bemade to the following examples that lie within the scope of theseclaims.

EXAMPLES Example 1 Formation of (Aminoalkyl)amide Compounds

An (aminoalkyl)amide compound was formed by reacting a metathesizednatural oil and a bis(aminoalkyl)amine. Diethylenetriamine (DETA)(106.18 grams (g)) and sodium methoxide (1.11 g) were combined in aflask equipped with a condenser, and the mixture was heated to 115° C.and stirred. To this mixture, metathesized soybean oil (MSBO; 250 g) wasadded dropwise.

Table 1 lists the reactants present in the reaction mixture. Thesaponification value (SAP) of MSBO was determined using the standardAOCS (American Oil Chemists' Society) procedure. The average molecularweight between ester groups in the MSBO was approximately56,100/SAP=56,100/210=267.2 Daltons.

TABLE 1 Reactants used to form (aminoalkyl)amide compounds Sodium MSBODiethylenetriamine methoxide molecular weight 210*  103.17 g/mol 54.02g/mol mass 250 g 106.18 g 1.11 g moles    0.9357 1.0292 0.0206equivalents 1 1.1 0.022 *saponification value

The mixture was maintained at 115° C. for 2 hours after the MSBOaddition was complete. The mixture was allowed to cool, and was thendissolved in diethyl ether, washed with a saturated sodium chloridesolution, and dried. The ether was removed from the product by rotaryevaporation to provide a mixture of monomers having at least two primaryamine functional groups and containing a group derived from the MSBO.

Characterization of the product by Fourier Transform InfraredSpectroscopy (FTIR) was consistent with full conversion of the estergroups of the MSBO to N,N-bis(aminoethyl)amide groups. While neitherdesiring to be bound by any particular theory nor intending to limit inany measure the scope of the appended claims or their equivalents, it ispresently believed that the product may be represented by Structures IIIand/or IV, above.

Example 2 Formation of Epoxy Thermoset

A polymer was formed by reacting bisphenol A diglycidyl ether with acompound having a plurality of primary amine functional groups. The(aminoalkyl)amide compound of Example 1 and bisphenol A diglycidyl etherwere combined, resulting in a hard epoxy polymer product.

The foregoing detailed description and accompanying drawings have beenprovided by way of explanation and illustration, and are not intended tolimit the scope of the appended claims. Many variations in the presentlypreferred embodiments illustrated herein will be apparent to one ofordinary skill in the art, and remain within the scope of the appendedclaims and their equivalents.

It is to be understood that the elements and features recited in theappended claims may be combined in different ways to produce new claimsthat likewise fall within the scope of the present invention. Thus,whereas the dependent claims appended below depend from only a singleindependent or dependent claim, it is to be understood that thesedependent claims can, alternatively, be made to depend in thealternative from any preceding claim—whether independent or dependentand that such new combinations are to be understood as forming a part ofthe present specification.

1. A compound having Structure I:

where R₁ and R₂ independently are C₂-C₁₂ alkyl groups, X₁ is a C₄-C₂₈alkyl or alkenyl group, and R₃ is selected from the group consisting ofH and a bis(aminoalkyl)amide group having Structure II:

where R₄ and R₅ independently are C₂-C₁₂ alkyl groups.
 2. The compoundof claim 1, where R₁, R₂, R₄ and R₅ independently are C₂-C₆ alkylgroups.
 3. The compound of claim 1, where X₁ is a C₈-C₂₂ alkyl oralkenyl group.
 4. The compound of claim 1, where X₁ is a C₁₀-C₁₆ alkylor alkenyl group.
 5. The compound of claim 1, having Structure III:

where X₂ is a C₄-C₂₈ alkyl or alkenyl group.
 6. The compound of claim 1,where R₃ is the bis(aminoalkyl)amide group.
 7. The compound of claim 6,where X₁ is a C₈-C₂₂ alkyl or alkenyl group.
 8. The compound of claim 6,where X₁ is a C₁₀-C₁₆ alkyl or alkenyl group.
 9. The compound of claim6, having Structure IV:

where X₃ is a C₄-C₂₈ alkyl or alkenyl group.
 10. An (aminoalkyl)amidecomposition, comprising: the reaction product of a metathesized naturaloil and a bis(aminoalkyl)amine.
 11. The (aminoalkyl)amide composition ofclaim 10, where the natural oil is selected from the group consisting ofvegetable oils, algal oils, animal fats, tall oils, derivatives thereof,and combinations thereof.
 12. The (aminoalkyl)amide composition of claim10 where the natural oil is selected from the group consisting of canolaoil, rapeseed oil, coconut oil, corn oil, cottonseed oil, olive oil,palm oil, peanut oil, safflower oil, sesame oil, soybean oil, sunfloweroil, linseed oil, palm kernel oil, tung oil, jatropha oil, mustard oil,camelina oil, pennycress oil, hemp oil, algal oil, castor oil, lard,tallow, poultry fat, yellow grease, fish oil, tall oils, andcombinations thereof.
 13. The (aminoalkyl)amide composition of claim 10,where the bis(aminoalkyl)amine is selected from the group consisting ofbis(2-aminopropyl)amine, N-2-aminopropyl-N-aminoethylmine,diethylenetriamine, and combinations thereof.
 14. The (aminoalkyl)amidecomposition of claim 10, where the metathesized natural oil comprisesmetathesized soybean oil, and the bis(aminoalkyl)amine comprisesdiethylenetriamine.
 15. The (aminoalkyl)amide composition of claim 14,where the reaction product comprises at least one of a compound havingStructure III:

where X₂ is a C₄-C₂₈ alkenyl group, and a compound having Structure IV:

where X₃ is a C₄-C₂₈ alkyl or alkenyl group.
 16. A method of making an(aminoalkyl)amide composition, comprising: forming a reaction mixturecomprising a metathesized natural oil and a bis(aminoalkyl)amine; andforming a product mixture comprising an (aminoalkyl)amide formed fromthe metathesized natural oil and the bis(aminoalkyl)amine.
 17. Themethod of claim 16, where the natural oil is selected from the groupconsisting of vegetable oils, algal oils, animal fats, tall oils,derivatives thereof, and combinations thereof.
 18. The method of claim16, where the natural oil is selected from the group consisting ofcanola oil, rapeseed oil, coconut oil, corn oil, cottonseed oil, oliveoil, palm oil, peanut oil, safflower oil, sesame oil, soybean oil,sunflower oil, linseed oil, palm kernel oil, tung oil, jatropha oil,mustard oil, camelina oil, pennycress oil, hemp oil, algal oil, castoroil, lard, tallow, poultry fat, yellow grease, fish oil, tall oils, andcombinations thereof.
 19. The method of claim 16, where thebis(aminoalkyl)amine is selected from the group consisting ofbis(2-aminopropyl)amine, N-2-aminopropyl-N-aminoethylmine,diethylenetriamine, and combinations thereof.
 20. (canceled)
 21. Themethod of claim 16, where the reaction mixture further comprises a base.22. (canceled)
 23. The method of claim 16, where the metathesizednatural oil comprises metathesized soybean oil, and thebis(aminoalkyl)amine comprises diethylenetriamine.
 24. The method ofclaim 16, where the product mixture comprises at least one of a compoundhaving Structure III:

where X₂ is a C₄-C₂₈ alkyl or alkenyl group, and a compound havingStructure IV:

where X₃ is a C₄-C₂₈ alkyl or alkenyl group.
 25. (canceled)